Treatment of textile or other materials



Patented Jan. 28, 1936 r TREATMENT Spondon,

tion of Delaware OF TEXTILE OR OTHER MATERIALS George Holland Ellis andRalph Charles Storey, near Derby, England, assignors to CelaneseCorporation of America, a corpora- No Drawing. Application May 28, 1931,Serial l1$o1540,800. In Great Britain February 20,

13 Claims.

This invention relates to the treatment of textile materials of naturalorigin and to the treatment of textile and other materials of artificialorigin, and more especially those made of or con- 5 taining celluloseesters or ethers, and is particularly concerned with the fixation ofinsoluble metallic compounds therein.

The fixation 'of insoluble metallic compounds in natural silk goods hasbeen practised for many years, mainly with the object of weighting thegoods. Such processes are not applicable to the treatment of materialsmade of or containing cellulose acetate or other cellulose esters orethers probably by reason of the water resistant character of thesegoods. Nevertheless processes have in the last few years been devisedfor the purpose of incorporating metallic compoundsin'such materials.These processes overcome the inherently small absorption exhibitedby\.the goods for metallic compounds by a previous or simultaneousswelling of-the goods either with an extraneous swelling agent or.bymeans of the weighting solution itself applied under suitableconditions. It was found that, apart from the improved propertiesdirectly attributable to the weighting as in the natural silk industry,the weighting of the cellulose ester or ether materials increases thesafe ironing point of the materials, obviously a very desirable object.

the material the latter is in general first treated with a metalliccompound, for example stannic chloride, and is then treated with aprecipitant for the tin or other metal. The fixation is customarilyeffected with cold or with warm fixing solutions for example at 60 C. Wehave found that when practised in this way the weighting attained raisesthe safe ironing point of cellulose esters or ethers approximatelyproportionally to the quantity of weighting substance incorporated inthe material, so that in order to obtain very high maximum ironingtemperatures considerable amounts of weighting arenecessary.

We have now found that the maximum ironing temperature of the materialsmay be very considerably increased with comparatively small amounts ofweighting compounds, provided that the latter are'incorporated in thematerial in a voluminous form, that is to say they'permeatesubstantially the whole of the substance of the material to which theyhave been applied. When the weighted material is incinerated avoluminous ash is obtained. Various means may be adopted to achieve thisresult and in general it appears necessary that notonly shall thematerial under In fixing the insoluble metallic compounds in treatmentbe thoroughly impregnated with the weighting metal itself, but inaddition thorough impregnation with the precipitant should be. effected.We have found that high temperatures for applying the precipitant or forthe fixation 5 with the precipitant are particularly conducive to thisresult. For example temperatures of over C., and particularlytemperatures of to 100 C. may be used. The best results obtained so farhave been produced by applying the fixing 10 solution at a temperatureof about to C. Another factor which comes into consideration inproducing the insoluble metal compound in the material in the form of avoluminous precipitate consists in applying the fixing solution and/or15 I the solution of the weighting metal in the form of a comparativelydilute solution. Thus solutions of disodium phosphate or trisodiumphosphate, or sodium sulphate, for example, may be used inconcentrations up to 15%, and prefer- 20 ably concentrations of 0.5 to 5or 10%. Preferably both these factors are utilized for the purpose ofobtaining the voluminous precipitates characteristic of the presentinvention.

The invention as already indicated is of great- 5 est value in itsapplication to textile or other materials made of or containingcellulose acetate or other esters of cellulose, for example celluloseformate, cellulose propionate, or cellulose butyrate, or made of orcontaining cellulose 30 ethers, for example methyl, ethyl or ,benzylcellulose, since an increase in the ironing point of these materialsconsiderably enhances their value. Films, sheets and like materials mayalso have their resistance to heat improved by means 35 of the presentprocesses, and this. particular application of the invention is of thegreatest advantage when used, as hereinafter described, in conjunctionwith a process adapted to fireproof the materials. The process may alsobe applied 40 to the treatment of natural silk goods and is of value inthe treatment of artificial cellulosic materials, for example viscose,cuprammonium and nitro cellulose artificial silks. ,In addition,materials containing any of the above fibres in associ- 45 ation witheach other and/or'in association with other materials, such as cottonorwool, may be treated.

The metal, a compound of which is to be incorporated in the goods inaccordance with the 50 present invention, may be any metal capable ofyielding insoluble compounds, for example tin, aluminium, barium,calcium, magnesium, chro mium and iron.; If desired, it may be chosen inaccordance with any object it is desired to achieve 55 acteristic of thematerials treated according to the invention. For example if a simpleweighting of the material is to be achieved, tin or other suitableweighting metals may be used, while if it is desired to colour the goodswith mordant dyes, mordant metals may be incorporated, for example tin,iron, chromium or aluminium. Again if in addition to'thehigh ironingpoint a delustering of 'the goods is required it is preferable to employmetals which canyield opaque metallic compounds in the materials, as forexample the alkaline earth metals, barium being particularly important.In this connection reference is made broadly to the description in U. S.o application No. 303,602 filed 1st September, 1928. As alreadyindicated the present processes may be' applied to the materials inconjunction with a treatment adapted tofireprgof the materials, that isto say to modify their properties in such a way that the materials donot propagate flame and preferably do not glow when a source of heatapplied to ignite them removed. This aspect of the invention is mostvaluable in connection with artificial silks and other artificialfibres, especially those made of or containing cellulose acetate orother organic derivatives of cellulose, including nitro acetate ofcellulose and also films and sheets and like materials. Nitro cellulosefilms and sheets may also be treated by the process. The fireproofingmay be effected in any convenient manner simultaneously with orseparately from the process for raising the ironing point or resistanceto heat. The best fireproofing agents to use are compounds or mixturesof compounds containing a volatile element or group of elements, forexample ammonia or I organic bases, and containing or leaving asubstance or residue capable of comparatively easy fusion. Thesubstances which are most valuable for this purpose are those describedin British patent No. 391,105, which consists of the borates orphosphates of volatile basesor ,mixtures of boric or phosphoric acidwith salts having volatile bases or of borates or phosphates with saltshaving volatile bases. Preferably such compounds or mixtures areemployed with salts of (ammonia and especially ammonium halides, as forexample ammonium bromide. Thus for instance the best agents which wehave yet found for this purpose are mixtures of ammonium borate withammonium bromide 'or of ammonium phosphate with ammonium bromide. Ifdesired the fireproofing treatment may be applied simultaneously withany part of the ironproofing treatment characteristic of the invention.We have however found it convenient to apply the fireproofing treatmentseparately from the ironproofing treatment characteristic of theinvention, and in fact to apply the fireproofing treatment subsequent tothe ironproofing" treatment, it being convenientto apply any desireddyeing or 001- curing treatment between the ironproofing and thefireproofing treatment.

It is desirable in applying high percentages of fireproofing substanceto the materials to be dried therein to employ in conjunction with thefire-v proofing substance, for example ammonium bromide and ammoniumphosphate, a suitable to electrolytes, so that they are compatible withthe solutions applied for fireproofing purposes.

soluble metallic compound adapted to yield on For this purpose we havefound that the modern wetting agents which are highly sulphonated areparticularly suitable, and especially highly V sulphonated aliphatichydrocarbons, acids or alcohols. The sulphonated amides of higher fatty5 acids, for instance the sulphonated ethylene diamide of oleic acid,are also suitable.

Any convenient method of application may be utilized to impregnate thematerials with the treatment with a suitable precipitant theironpr'oofing compound of the invention. In the case of natural silkgoods or artificial cellulosic materials, simple impregnation withsoluble salts of the desired metals is usually suflicient. When treatingmaterials made of or containing cellulose acetate or other celluloseesters or ethers, special measures have in general to be taken tointroduce the metals in a satisfactory manner, and reference is made toU. S. Patents Nos. 1,631,-

062, 1,731,298, 1,806,048, 1,817,741, 1,821,464 and 1,867,658 and U. S.applications S. Nos. 143,789 filed 23rd October, 1926, 228,506 filed24th October, 1927, and 406,537 filed 11th November, 1929 The metal saltsolution used to apply the metal may itself be a swelling or gellingagent for the material, as for example in the case of stannic chloride,stannic chlorothiocyanate or barium thiocyanate, or a gelling orswelling agent may be caused to act upon the material eithersimultaneously or prior to the treatment with the metallic saltsolution. A combination of such methods of increasing the. absorptivepower of the fibre or material for the metal salt may be employed.Examples of suitable gelling or swelling agents for cellulose esters orethers are given in the patents referred to. They may for example 40 beaqueous solutions of thiocyanates, of glycollic acid, lactic acid,acetic acid, ethyl alcohol,

acetone, diacetone alcohol, diacetone phenol,

'hydroquinone or other water soluble phenols or polyhydric phenols, themono and di-ethers or esters or ether-esters of ethylene glycol or otherglycols or of polyolefine glycols, e. g. glycol mono methyl ether,glycol mono. ethyl ether, glycol mono acetate, and methyl-glyco1 monoacetate or diethyl lactate or other ester swelling agents.

The solutions of the soluble metal compounds I may be applied by simplebath treatments orby local application of the metal may be achieved,

for example, by printing or spraying methods.

In the case of artificial materials, a further methodforimpregnatingfithe materials with the metal consists in incorporating acompound of the metal in question in the'spinning. solution used for themanufacture of the materials. Such a method is described in US.application S. No. 455,969 filed 26th May, 1930. The spinning solutionsmay be spun by dry or wet methods, the coagulating bath in the lattercase being so chosen that substantial elimination of the metal from thefilaments or other products does not take place.

The conditions under which the fixing solution is applied or under whichthe fixing is eifected is the factor which affords the most valuablemeans of achieving the voluminous precipitate or precipitates yieldingvoluminous ash characterisuiiscontinuously ning by dry or wet methods.

tic of the invention. High or comparatively high fixing temperatures,especially when used in conjunction with the application of theprecipitant or weighting metal solution in relatively dilute solution,afiord the most suitable means of carrying the present'invention intoefiect. Any suitable precipitants may be used, for example disodiumhydrogen phosphate or trisodium hydrogen phosphate (especially when themetal has been applied by padding; spraying or other mechanicalimpregnation methods without subsequent washing as described in U. S.application S. No. 406,537 filed 11th November, 1929), ammoniumphosphates, sodium sulphate, particularly for use with barium as themetal, and sodium carbonate, more especially for use when mordant metalsare applied. Similarly, instead of sodium or ammonium salts, othersoluble salts may be employed. If it is desired to reduce thewater-permeability of the goods, soaps or the corresponding, acids maybeused as the precipitants as describedin U. S. applications S. Nos.374,288 filed 27th June, 1929 and 378,821 filed 16th July, 1929.

The precipitants may be applied in the form of a bath, or again as withthe metal compound itself, may be applied by spraying, printing, paddingor other mechanical impregnation methods, and reference is made to ofsuch processes in U. .8. application S. No. 406,537 filed 11th Novembe1929 and Patent No. 1,847,816. .The best results are obtained byeffecting the fixation at comparatively high temperatures, such as 80 to90 C. These temperatures may be achieved either during the actualapplication of the fixing or precipitating solution, or the goodscarrying the metals may be first impregnatedwit-h the fixing solutionand subse quently raised to the desired temperature to effect thefixation. Thus the invention contemplates not only bathtreatments at thehigh temperatures. but in addition contemplates applying theprecipitating solution by padding, spraying or other methods either athigh temperatures or at low temperatures followed by fixation -at hightemperatures. If the goods are liable to be delustered at thetemperature used for the fixation, preventive measures may be adopted ifsuch delustering is not desired, as for example by the use of salts orsugars as described in U. S. Patent No. 1,765,581 and U. S. Patent No.1,808,061. In the case of incorporating a soluble metal compound in thespinning solution used for the manu facture of artificial materials, theprecipitant may be contained in the coagulating medium when using wetspinning processes or in a subsequent treatment bath, applied eithercontinuously or with the spinning, when spin- By the above means theweighted material yields upon incineration a very voluminousv ash, sothat the whole of the substance of the material may be presumed to beimpregnated with the insoluble metallic compound. This is probablyresponsible for the very high*ironing points obtained. We find in factthat by means of the present invention the ironing point of a celluloseacetate fabric may be raised by 3 or 4 times as much as when thematerials are weighted by the previous methods with two or three timesthe amount of the weighting agent. Thus with a cellulose acetate fabricwhich has a normal safe ironing point of 220 to 230 0., whereas theknown weighting treatments may raise the safe ironthe detaileddescription off well, first hot and then ing point to 260 to 275 C., thesafe ironing point may be raised by means of the present invention to300 0., and in fact the fabric or other material may remain unmelted atas high as 340 or 350 or even 360 C., and this with an ash of 0.5 to-2%, and especially 1 to 115%. When it is considered that cotton isreadily scorched at a temperature of 260 to 280 C., the extreme value ofthe present invention in the treatment of materials of cellulose acetateor other cellulose esters or ethers will readily be appreciated. Suchmaterials having an ironing point above 260 to 280 C. are entirely novelproducts and form an important part of the present invention.

As already indicated, the materials treated in accordance with thepresent invention may have various properties depending upon the type ofinsoluble metallic compound which has been incorporated therein. Forexample they may be delustered due to the presence of an opaque metallicsalt, they may have the property of fixing mordant dyestuffs to obtainthe true lake shades, or they may have improved impermeability to water,particularly if insoluble metallic soaps have been fixed therein inaccordance with the process claimed broadly in U. S. applications filed16th July, 1929.

In addition to their affinity for the dispersed insoluble colours andaffinity for mordant colours depending on whether or not a mordantcompound has been applied, the materials may have acquired an afiinityfor a large number of direct and acid dyestuffs, which is especiallyuseful from the point of view of obtaining discharge effects thereon.Cellulose ester materials may, previous or subsequent to the applicationof the weighting metal, be saponified as described in U. S. applicationS. No. 363,706 filed 16th May, 1929, such saponification being effected,if desired, simultaneously with the fixation of the metal, for exampleby fixing with a solution of trisodium phosphate at a suitableconcentration, or with any other suitable precipitant in conjunctionwith caustic alkali or other saponifying agent. The materials may thenexhibit an afiinity for direct cotton colours, vat colours of all kinds,the sulphur colours and mordant colours, both natural and artificial,and reference is made to U. S. application S. No. 363,706 filed 16thMay, 1929 for further details in this respect and also for details ofobtaining discharge effects upon materials so coloured.

The following examples illustrate the invention but they are not to beconsidered as, limiting it in any way:-

Example 1 ,the batching operation. They are then batched at G. for 4 to5 hours, after which the fabric is passed withbut intermediate washinginto a bath of 30:1 volume ratio containing a 5% solution of trisodiumphosphate at 85 C. The fabric is treated in this bath for 10 minutes,washed cold, and finally soaped in a solution containing 1 gram perlitre of soap at C. ;for 15 minutes. The fabric S. Nos. 374,288 filed27th June, 1929 and 378,821

treated in this manner gives an ash of 1.5 cal- 3 culated as SnO-z.

Example 2 justed so that the fabric feels quite 'dry on emerging'. Thefabric is then passed directly into water at 90 to 100 C. for 10minutes, treated at the same temperature in a bath containing 37% oftrisodium phosphate on the weight of the goods and a volume ratio of :1for 15 to minutes.

The goods are then washed ofi thoroughly, and finally soaped in asolution containing-1 gram per litre of soap for 15 minutes at 45 C. Thefabric so treated has acquired a matt appearance and is analogous inproperties to that described in Example 1.

The fabric may then be dyed by any suitable method, as for example bymeans of the dispersed insolubie colours now customarilyapplied to cel-'lulose acetate.

litre 0t ammonium bromide, 100 grams per litre" of ammonium phosphateand 50 grams per litre 3G of Igepon A and dried without washing.

Example 3 A fabric is treated exactly as described in Ex ample 2 withthe exception that instead of 20:1

bath containing 37% on the weight of the goods Erample 4 A mixed liningfabric composed of cotton warp and cellulose acetate weft yarns isprocessed ex actly as described in Examples 1, 2 and 3, Greatly enhancedresistance to ironing and hot pressing treatments renders the fabricparticularly valuable in practical usage for lining purposes.

What we claim and desire to secure by Letters Patent is: v i 1 v1.Process for increasing the heat resistance of materials comprising anorganic ester of cellulose, which comprises incorporating therein asmall proportion of an insoluble compound of a metal by impregnating thematerial with a comof the metal and fixing the metal therein, by' meansof a dilute solution of an alkaline. fir.-

ing agent, at a temperature of 75 to 100 C., the

small proportion of an insoluble compound of a metal by impregnating thematerial with a compound of the metal and fixing the metal therein, bymeans of a dilute solution or an alkaline fixing agent, at a temperatureof 85 to 100 C., the conditions of treatment beingsuch that the amountof metal compound incorporated in the material imparts thereto an ashcontent of 0.5 to 2%.

3. Process for increasing the heat resistance of materials comprising anorganic ester of cellulose, which comprises incorporating therein asmall proportion of an insoluble compound of After such treatment thefabric is padded in a solution containing "150 grams per tin byimpregnating the material a compound of tin and fixing the tin therein,by means of a dilute alkaline solution, of a phosphate, at atemperature-oi 85 to 100 C., the conditions of treatment being such thatthe amount of tin compound incorporated inthe material imparts theretoan ash content of 0.5.to 2%.

4. Process for increasing the heat resistance of 4 materials comprisingcellulose acetate, which comprises incorporating therein a smallproportion of an insoluble compound of a metal by impregnating thematerial with a compound of the metal and fixing the metal therein, bymeans of a dilute solution of an alkaline fixing agent,.at a temperatureof 75' to 100 C., the conditions of treatment being such that the amountof metal compound incorporated in the materialimparts there- :whichcomprises incorporating therein a small proportion of, aninsolublecompound of tin by impregnating the material with a compound .of tin andfixing the,tin therein, by means of a dilute alkaline solution of aphosphate, at a tom perature 0105 to 100 C., the conditions of treatmentbeing such that the amount of tin compound incorporated in the materialimparts there-- ment being such that the amount of tin compoundincorporated in the material imparts thereto an' ash content of 0.5 to2%.

'7. Process for increasing the heat resistance of textile matericomprising cellulose acetate, which comprises incorporating therein' asmall proportion of an insoluble compound of tin byimpregnating thematerial with a compound of tin and fixing the tin therein, by means ofa 5 to 10% solution of trisodium phosphate, at a temperature of 35 to100 C., the conditions of treatment being such that the amount of tincompound incorporated in the material imparts thereto an ash content of0.5 to 2%.

5 8. Process for increasing the heat resistance of textile materialscomprising cellulose acetate, which comprises incorporating therein asmall proportion of an insoluble compound of a metal by impregnating thematerials with a dilute solution of a compound of the metal and fixingthe metal therein, by means of a dilute solution of an alkaline fixingagent, at a temperature of '75 to 100 C., the conditions of treatmentbeing such that the amount of metai compound incorporated in thematerial imparts thereto an ash content of 0.5 to 2%.

9. Process for increasing the heat resistance of textile materialscomprising cellulose acetate, which comprises incorporating therein asmall proportion ,of an insoluble compound of .'tin by impregnating thematerials with a dilute solution parts thereto an ash content of 0.5 to2%.

' Process for-increa ing the heat resistance of textile materialscomprising cellulose acetate which comprises incorporating therein asmall proportion of an insoluble tin compound by impregnating thematerial with an aqueous solution containing 125 grams per litre ofstannic chloride crystals and 100 grams per litre of ammoniumthiocyanate and fixing the tin therein by means of a solution oftrisodium phosphate of substantially 5% concentration at a temperatureof 85 to 100 C., the conditions of treatment being such that the amountof tin compound incorporated'in the material imparts thereto an ash content of 0.5 to 2%.

11.'Textile materials comprising organic derivatives of cellulose .andcontaining a small proportion of an insoluble metallic compound in aform yielding on incineration a voluminous ash of 0.5 to 2%, and havinga safe ironing point oi vat least 300 C.

containing a small proportion of an insoluble tin 10 compound, saidmaterials yielding on incineration a. voluminous ash of 0.5 to 2%, andhaving a safe ironing point of at least 300 C.

GEORGE HOLLAND ELLIS. RALPH CHARLES STOREY.

